Polyhydric alcohol-carboxylic or



Reissued Sept. 21, 1937 -UNITED STATES PATENT OFFICE.

Israel Rosenblum, New York, N. Y.-

No Drawing. Original'No. 1,969,761, dated August 14, 1934, Serial No. 441,731, April 4, 1930. Renewed October 17, 1933. Application for reissue June 2'7, 1936, Serial No. 87,807

20 Claims.

My invention relates to synthetic resins and has for its object to produce resinous condensation products of great complexity and extraordinarily high molecular weight with the aid of a 5 polybasic inorganic acid or its anhydride.

It is also an object of the present-invention to produce synthetic resins of ready solubility in the common, solvents, such as mineral spirits, toluol, ethyl acetate, varnish oils, etc., and of substantially neutral reaction, good consistency and body, which are compatible with nitrocellulose and other cellulosic lacquers and may be used in conjunction therewith, and also witha great variety of natural and synthetic gums used in the lacquer and varnish industry.

It is well known that polyhydric alcohols, such as glycerol, may be either completely or partially esterifled with monobasic or polybaslc acids to produce esters which, in certain cases, are of resinous character or can be condensed or polymerlzed into resinous or approximately resinous substances by more or less prolonged heating at elevated temperatures. during the formation of many of the synthetic resinous products are not thoroughly understood, but it is probable that duringthe first stages of the-reaction a part of the polyhydric alcohol is under certain conditions only partially esterified (especially when an excess of the alcohol is present), and that during the subsequent heating the free hydroxyl groups of two or more molecules condense and become united through an oxygen bond to form a more complex molecule.

According to the present invention, a plurality of molecules of partially esterifled polyhydric alcohols (which may or may not themselves be of resinous character) are united or condensed with the aid of an inorganic polybasic acid or its an- 40 hydride which directly forms the bond between such molecules. In this way, a plurality of large organic molecules may be condensed by, an inorganic acid of relatively low molecular weight,

The reactions occurring and composed of a polyhydric alcohol, a monobasic or polybasic organic acid, a polybasic inorganic acid, and the reaction product of a phenol, an aldehyde, and the organic salt of a metal.

In order that my invention may be better understood, I shall,describe the same in connection with the production of complex resins from phthalic acid (or anhydride) glycerol, boric acid, and an acidic organic material, including the acidic condensate obtained by condensing phenol and formaldehyde in the presence of an organic salt of zinc, such as zinc abietate, and of a natural resin, such as rosin.

Phthalic acid may be caused to be combined in any known manner with an excess of glycerol to produce hydroxy-esters, of which the following simple compounds are illustrative:

H H A (EHzOH Other compounds are doubtless produced but only these are represented for the sake of simplicity as they are sufllcient to illustrate the nature of the present invention. Themixture of hydroxy-esters is then caused to react with boric acid (H3303) at about 140-150" 0., whereupon condensation takes place producing, among other compounds, the following comparatively simple compound (assuming that one molecule of boric acid reacts with a molecule of each of the hydroxy-esters formulated above):

The above compound probably represents only an intermediate product, for the two free bydroxyls may condense with the hydroxyl groups of similar products or of non-boronized hydroxyesters, either directly or with the aid of additional 'boric acid. It will thus be seen that extreme complexity of molecular structure may be obtained in a number of ways with the aid 01 the inorganic acid The boronized condensates obtained as indicated above are characterized by great body, a

property which has heretofore been imparted to glycerol-phthalic acid resins only with the aid of additions, such as rosin.

Products of greater solubility and flexibility may, in accordance with the present invention, be obtained by treating the boronized hydroxy-esters with acids until the same are substantially neutral. Organic acids of any kind may be em p yed, such asacetic, succinic, tartaric, benzoic,

phthalic, etc., and also resin acids, either natural or synthetic. Excellent results are obtained by the use of the higher aliphatic acids, such as oleic, linoleic, linolenic, ricinoleic, stearic, palmitic, and other acids obtainable from drying and non-drying oils and from fats; and where I employ such oil and fat acids, 1 may cause the acids to react 'with the polyhydric alcohol prior tothedibasic acid, as illustrated in Examples 2 and 3 below. In general, I prefer to employ rosin or other natural resin (which is, of course, acidic in nature) in conjunction with any of the acids just specified. Improved results are generally; obtained if the natural resin, if used, is first cracked or drydistilled, as by heating to a temperature of about 260 C. or above. alone or together with linoleic or any of the other acids mentioned, a condensation product of phenol, formaldehyde, a natural resin, such as rosin, and an organic salt, such as a zinc soap, specifically zinc abietate, as described in my above-mentioned patent. The acidic compounds lust enumerated will combine with the boronized hydroxy-esters of glycerol and phthalic acid, and at least Partially neutralizethe same, thereby producing extremely complex esters of glycerol with phthalic acid, boric acid, and one or more of the other acidic organic bodies mentioned above.

The treatment of the boronized hydroxy-esters withthe fatty acids mentioned above are described and, excepting the treatment with the phenol-formaldehyde condensation product, claimed in my co-pending application, Ser. No. 438,901, filed March 25, 1930. The present application is in the nature of a division of such earlier filed case and is directed to the treatment of the boronized hydroxy-esters with a phenol aldehyde condensate and to the products obtained thereby.

As indicated above, and as preferably carried out, the reaction between the partial ester of lycerol and phthalic acid and the boric acid is made to take place under such proportions and conditions that the resulting product contains freebasic hydroxyl groups. As is well known, the reaction product of phenol and formaldehyde at an advanced, though still soluble, stage of condensation is usually of acidic nature, particularly if the condensation is made to take place in the presence of rosin or other natural resin, I have found that the hydroxy boronized condensate can be made to combine with the acidic phenolic condensate to produce a substantially neutral, highly complex resin having very valuable properties,

. particularly with regard to solubility, body, luster and compatibility with cellulosic and other lacquers and varnishes.

The reaction may be made to occur in steps, as by first treating the phthalic acid with glycerol and then reacting the hydroxy-esters so produced with boric acid and finally heating the boronized hydroxy-esters with the phenolic condensate until a substantially neutral product is I may also employ, either.

obtained; or'else all of the ingredients in proper proportions may be made to react simultaneouslys Instead of combining the condensate of boric acid with the monoand tetra-hydroxy glycerolphthalic acid esters (or other hydroxy-esters) directly with the phenolic condensate, the free basic hydroxyls of these boronized esters may be combined with the acidic compounds obtained by condensing with an excess of boric acid the hydroxy-esters obtained by partially neutralizing glycerol with an acidic phenolic condensate, preferably one formed in the presence of an organic salt. In this way, complex compounds are obtained in which what may be regarded as a nucleus composed of an ester of glycerol and phthalic acid is joined through boron bonds to one or more other glycerol-phthalic acid esters and to one or more glycerol esters of phenolic I may partially, neutralize it with such condensate together with rosin or other natural resin, or together with any of the other organic acids listed hereinabove. In general, I prefer to use, in place of the rosin as it is commercially available, rosin' which has been heated or cracked in the presence of an organic zinc (or other metal) 5 salt-phenol-aldehyde condensate. By the use of such zinc-phenol-aldehyde condensate, the product is made more resistant, while at the same time the formation of compounds, which crystallize out from ethyl acetate solution and consequently are not colloidal or film-forming, is prevented. It will be understood that, in place, of rosin, other resins, such as the fossil resins, may be employed which are similarly dry-distilled or cracked.

By the above procedure, extremely complex resins are obtained which are highly weatherand water-proof, have excellent body and are compatible with cellulosic lacquers. My novel boronized condensates produce varnishes having a very glossy and lustrous surface. They also make excellent wood fillers- Condensates of somewhat different properties may be obtained, according to my invention, by treating an excess of glycerol with boric acid and then reacting the hydroxy-esters so obtainedwith a synthetic resin 'of acidic nature, such as a phenol-formaldehyde resin, and preferably-;,one produced in thepresence of rosin and an organic salt of zinc or other metal, such as calcium,g lead, tin, or any of the other metals mentioned in -my United States Patent No. 1,809,570. Instead of first boronizing the glycerol, all of the reacting compounds may be mixed together and'heated. By the use of boric acida resin of improved properties is obtained in which the condensation is more complete. p

Several modes of carrying out my are described her'einbelow, but it will be understood that the examples are given by way of illustration only and are not to be construed in a limiting sense. I

Example 1.'-148 grams of phthalic anhydride, 31 grams of boric acid and grams of glycerol are heated together with 50 grams of the acidic invention condensate obtained by condensing phenol, formaldehyde, and an organic salt of a metal, such as who, in the presence of a solvent or flux, such as natural resins and drying and 'non-drying oils, aswiescribed in my aforementioned United States patent, and grams of stearic acid. The temperature is maintained at about 240 C. until a sample is found to be completely soluble in toluol, indicating the absence of free glycerol. The resin obtained is compatible with solutions of nitrocellulose.

Example 2.280 grams of linoleic acid, 200 grams of glycerol (98% pure), and 31 grams of boric acid are heated at about 180 C. for two hours. There are then added 74 grams of phthalic anhydride and 300 grams of an organic zinc salt-phenol-formaldehyde condensate (prepared as described in my aforementioned patent). The temperature is permitted to rise to about 230 C.

and kept at such value until a sample of the product forms a clear solution in toluol.

Example 3.The procedure outlined under Example 2 is followed except that, in place of part of the zinc salt-phenol-formaldehyde condensate, there is used an equivalent quantity of dry-distilled or non-distilled rosin or any drydistilled fossil gum.

Example 4.-280 grams of linoleic acid, 200 grams of glycerol (98% pure) and 62 grams of boric acid are heated to about 180 C. for two hours. There are then added 600 grams of the acidic condensate obtained from the interaction of 60 grams of phenol, 60 grams of formaldehyde, 3 grams of zinc abietate (or equivalent amount of oxide), and. 600 grams of rosin, as described in my above-mentioned patent. As indicated in said patent, there may be used the organic salts of other metals than zinc, for example the acetate, benzoate, stearate, palmitate, abietate, etc. of calcium, barium, strontium, magnesium, tin, lead, etc. The temperature is permitted to rise to about 230 C. and kept at that value until a sample of the product forms a clear solution in toluol.

Example 5.The same as Example 4 except that no zinc abietate is used in the preparation of the phenolic condensate.

If desired, an excess of fatty acids may be employed in the examples given above because the same are compatible with my noved boronized condensates.

As indicated above, any suitable polyhydric alcohol other than glycerol may-be used, such-as glycol, mannitol, etc.; in place of phthalic acid any other organic acid, or its anhydride, monobasic or polybasic, may be used, such as succinic, tartaric, malic, maleic, etc., or any of the high molecular weight acids mentioned above; and in place of boric acid any other suitable polyhydric inorganic acid, such as -tel1uric,-phosphoric, arsenic, silicic acids, etc., or their anhydrides, may be employed. If desired, the reactions described hereinabove may be made to take place in the presence of a natural resin, preferably drydistilled, which may act as a solvent, or may supply bn of the reacting acids.

I desire to call attention to my copending ap- .acid, as one of the reacting acidic materials. The

claims of the present application are either drawn generically to acids of both the open chain and 'cyclic types, or are specific to an aromatic acid (phthalic acid) Variations may be resorted to within the scope of the appended claims without departing from the spirit of the invention.

I claim:

1. The method of producing complex resinous condensation products, which comprises heating a polyhydric alcohol, a carboxylic organic acid, a weak polybasic inorganic acid and an acidic phenol-aldehyde resin until a substantially neutral, clear condensate soluble in toluol is obtained.

2. The method of producing complex resinous condensation products, which comprises heating a polyhydric alcohol, an acid obtainable by hydrolysis of a member of the group consisting of oils and fats, a polybasic carboxylic organic acid, a Weak polybasic inorganic acid, and an acidic phenol-aldehyde resin until a substantially neutral, clear condensate soluble in toluol is ob-v tained.

3. The method of producing complex resinous condensation products, which comprises heating a polyhydric alcohol, an acid obtainable by bydrolysis of a member of the group consisting of oils and fats, a, carboxylic organic acid other than said first acid, a weak polybasic inorganic acid, and an acidic phenol-formaldehyde resin until a substantially neutral, clear condensate soluble in toluol is obtained. a

4. The method of producing complex resinous condensation products, which comprises heating a polyhydric alcohol, phthalic acid, a weak polybasic inorganic acid, and an acidic phenol-aldehyde resin until a substantially neutral, clear condensate soluble in toluol is obtained.

5. The method of producing complex resinous condensation products, which comprises heating glycerol; a drying oil acid, phthalic acid, a weak polybasic inorganic acid, and an acidic phenolaldehyde resin until a substantially neutral, clear condensate soluble in toluol is obtained.

6. The method of producing complex resinous condensation products, which comprises heating glycerol, phthalic acid, a fatty oil acid, boric acid, and an acidic phenol-aldehyde resin until a substantially neutral, clear condensate soluble in toluol is obtained.

7. The method of producing complex resinous condensation products, which comprises heating glycerol, a drying oil acid, phthalic acid, boric acid, and an acidic organic materialcomprising a phenol-formaldehyde condensate until a substantially neutral, clear condensate soluble in toluol is obtained. I

8. The method of producing complex resinous densate until a substantially neutral, clear condensate soluble in toluol is obtained.

9. The methodwhich comprises partially esterifying a quantity of glycerol with a carboxylic organic acid in the presencefof a weak polybasic inorganic acid in quantities less than the theoretical quantity requiredcompletely to neutralize the glycerol, whereby hydroxyl-containing esters are produced, and heating the resulting mass with a phenol-aldehyde condensate of acidic reaction at elevated temperatures to effect at least F partial neutralization of the esters by said condensate. f

10. The method which comprises heating a partial fatty oil acid ester of glycerol having free hydroxyl groups with a quantity of a weak polytralization of the first condensate by the polybasic inorganic acid which is less than the theoretical quantity required to neutralize all of the hydroxyl groups, whereby a condensate having still free hydroxyl groups is obtained, and

then reacting said condensate with a polybasic carboxylic acid and a soluble acidic condensate of a phenol and an aldehyde at elevated temperatures to effect at least partial neutralization basic acid and by the other condensate.

12. A soluble polyhydric alcohol-carboxylic organic acid-weak polybasic inorganic acid-phenolaldehyde resin condensation product.

13. A soluble resinous condensation product having the general formula R,(O--R)I, wherein R is a weak polybasic inorganic acid-forming element, R the residue of a basic hydroxylated organic substance containing a phenol-aldehyde condensate, and x has the value of two or more.

14. A soluble resinous condensation product having the general formula R-(O-R')x, wherein R is a weak polybasic inorganic acid-forming element, R the residue of a basic hydroxylated organic substance including a partial glycerol ester of an acidic phenol-aldehyde condensate, and :1: has the value of two or more.

substances, including a partial ester of glycerol and phthalic acid, and a partial ester of glycerol anda phenol-formaldehyde-carboxylic-acid zinc salt-rosin condensate.

17. A soluble resinous condensation product comprising a glycerol-organic acid-boric acid condensate neutralized with a phenol-formaldehyde-carboxylic acid salt condensate.

18. A soluble condensation product produced I by reacting a polyhydric alcohol, a monobasic aliphatic acid material including an acid ob-' tained by hydrolysis of a member of the group consisting of oils and fats, a polybasic carboxylic organic acid, a weak polybasic inorganic acid, and a phenol-aldehyde resin.

19. A soluble resinous condensation reaction product of boric acid, the basic hydr0xy1-containing partial glycerol ester of a drying oil acid, phthalic acid and an acidic condensateo! a phenol, formaldehyde, and' rosin.

20. A soluble resinous condensation reaction product of boric acid, glycerol, an acid obtained by hydrolysis of a. member of the group consisting of oils and fats, phthalic acid and a condensate of a phenol, formaldehyde, a a carboxylic acid, and rosin.

ISRAEL ROSENBLUM.

zinc salt of 

